Use of the Cationic Fragments [Ru(η5-C5H5) (MeCN)3]+ and [M(η6-C6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as Ionic Coupling Reagents in the Synthesis of the Clusters [Os4M2(CO)12(η6-C6H5R)], [Os4M(CO)12(η6-C6H6)(Au2dppm)] and [Os5Ru(CO)15(η5-C5H5)(AuPPh3)]*

Journal of Cluster Science - 2005
Muna R. A. Al-Mandhary1, Radchada Buntem1, Cheryl L. Doherty2, Andrew J. Edwards1, John F. Gallagher1, Jack Lewis1, Chi-Keung Li1, Paul R. Raithby3,2, M. Carmen Ramirez de Arellano1, Gregory P. Shields1
1Department of Chemistry, University of Cambridge, Cambridge, UK
2Department of Chemistry, University of Bath, Bath, UK
3CCLRC, Daresbury Laboratory, Daresbury, UK

Tóm tắt

The clusters [H2Os4M(CO)12eta6-C6H6)] (M=Os, Ru) may be deprotonated to generate anions [Os4M(CO)12eta6-C6H6)]2- which react with [M′eta6-C6H5R) (MeCN)3]2+(M′=Os, Ru; R=H, Me) to give the bicapped tetrahedral clusters [Os4(CO)12MM′eta6-C6H5R)2]. Whereas [Os4(CO)12M2eta6-C6H6)2] (M=Os, Ru) have one Meta6-C6H6) unit in a site connected to three other metals, {3}, and one in a site connected to four other metals, {4}, [Os4(CO)12OsRueta6-C6H6)2] has the Rueta6-C6H6) unit in the {3} site irrespective of whether the Os or Ru anion is capped. Coupling of these anions with Au2dppm yields [Os4M(CO)12eta6-C6H6)(Au2dppm)] (M=Os, Ru), which have the arene ligand in the axial site of a trigonal bipyramid and the digold unit capping two faces. Reduction of [H2Os5(CO)15] with K/Ph2CO and coupling with [Rueta5-C5H5)(MeCN)3]2+yields the monoanion [Os5(CO)15Rueta5-C5H5)]− which reacts with [AuPPh3]+ generating [Os5(CO)15Rueta5-C5H5)(AuPPh3)] with the “Ru(C5H5)” unit in the terminal {3} site.

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